Cmp method for forming smooth diamond surfaces

ABSTRACT

A method of chemical mechanical polishing (CMP) a diamond containing surface includes providing a slurry including a plurality of particles, at least one oxidizer, and at least one acid, wherein the slurry has a pH≦3 or pH greater than 11. At least an outer surface of the plurality of particles is softer than the diamond surface or the particles are diamond particles averaging less than (&lt;) 2 μm in size. The diamond surface is pressed with respect to a polishing pad providing a Shore D Hardness less than 99 having the slurry in between while rotating the polishing pad relative to the diamond surface to form a smooth diamond surface having a root mean square (rms) surface roughness less than 15 nm.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. Non-Provisionalpatent application Ser. No. 13/669,955 filed Nov. 6, 2012, entitled“SMOOTH DIAMOND SURFACES AND CMP METHOD FOR FORMING”.

FIELD

Disclosed embodiments relate to chemical mechanical polishing (CMP) ofdiamond surfaces to form smooth diamond surfaces and electronic devicesthat include at least one smooth diamond surface layer.

BACKGROUND

Diamond is an allotrope of carbon, where the carbon atoms are arrangedin a face-centered cubic crystal structure called a diamond lattice.Crystalline diamond can be classified based on grain size into supernano-crystalline (grain size less than 10 nm), nano-crystalline (grainsize between 10 nm and 250 nm), micro-crystalline (grain size from 250nm to 250 microns) and single crystalline diamond (grain size greaterthan 250 microns). The diamond can exist in thin films (film thicknessless than 20 microns), thick films (film thickness greater than 20microns to 200 microns), or bulk materials (thickness greater than 200microns). Diamond films and bulk materials can coexist with graphiticsp2 phases. Single crystal diamond films can have (100), (110), (111),or other crystal orientations.

Diamonds are adapted for many uses because of exceptional physicalcharacteristics. Notable are its extreme hardness and high thermalconductivity (900 to 2,320 W·m⁻¹·K⁻¹), as well as a wide bandgap andhigh optical dispersion. The thermal conductivity of diamond issignificantly higher than any other known material, which makes diamondthin film substrates an ideal choice for thermal challenges posed byapplications including (1) miniaturization of electronic devices, (2)high brightness light emitting diodes (LEDs), (3) laser diodes and (4)high power (e.g., 500 W/mm²)/high frequency devices, (5) high frequencydevices, and (6) acoustic devices. Applications well-suited for diamondlayers include MEMS (micro electro mechanical structures), NEMS (nanoelectro mechanical structures) and diamond-based power electronicdevices. Diamond can also be used for conditioning the pads in chemicalmechanical polishing (CMP) processing, or as a cutting tool material.

To harness the unique properties of diamond, in applications such as forelectronics, it is desirable to have ultra-smooth diamond surfaces sinceultra-smooth surfaces decrease friction, increase thermal conductivity,and improve integration compatibility. The applications will generallydepend on a combination of properties. For example, application ofdiamond as a substrate for electronic packaging takes advantage of itsvery high thermal conductivity for efficient heat dissipation, very highelectrical resistivity for excellent electrical insulation and lowpermeability for environmental protection of the devices.

However, despite its desirability, ultra-smooth diamond surfaces haveremained an unmet need. As known in the art, as-deposited low pressurevapor phase diamond films are very rough, with a typical average surfaceroughness of at least 4 nm up to several hundred microns, depending onthe thickness of the film and the grain size of the film.

Traditional CMP methods have not generally been suitable for polishingof diamond films. This is primarily because of the extreme hardness andchemical inertness of diamond, which results in standard chemistries andparticle-based CMP achieving very low or essentially no removal rate fordiamond. Non-CMP methods have also been disclosed for planarization ofdiamond, including (1) laser polishing (2) ion beam polishing, (3)polishing using molten salts, and (4) diamond-diamond abrading. Suchmethods are neither cost-effective, nor viable for manufacturability atan industrial level. Further, such processes do not reduce the averagesurface roughness to a level suitable for use in semiconductor devicemanufacturing, such as <20 nm root mean square (rms). Moreover, the useof diamond particles without chemical additives can create sub-surfacedamage which can result in poor quality epitaxial growth thereon andreduced thermal conductivity.

SUMMARY

This Summary is provided to introduce a brief selection of disclosedconcepts in a simplified form that are further described below in theDetailed Description including the drawings provided. This Summary isnot intended to limit the claimed subject matter's scope.

Disclosed embodiments include chemical mechanical polishing(CMP)-methods for processing diamond surfaces that provide smoothdiamond surfaces. A smooth diamond surface is defined herein as having:(i) a root mean square (rms) surface roughness less than (<) 15 nm foran average grain size greater than (>) 0.5 μm, an rms surface roughnessless than (<) 10 nm for an average grain size between 50 nm and 0.5 μm,and an rms surface roughness less than (<) 5 nm for an average grainsize less than (<) 50 nm, and (ii) a polishing damage index (PDI) ofless than (<) 10⁹/cm².

The smooth diamond surface can be on a diamond film/layer with athickness ranging from 10 nm to 200 microns, or on a bulk single crystaldiamond material with a thickness exceeding 200 microns. As used herein,the diamond material is in the form of a thin film if the thickness isless than 20 microns, and is in the form of a thick film if thethickness is between 20 microns to 200 microns.

The diamond surface can also be in form of composite, for example >0.2micron size diamond particles on the surface of a metallic, ceramic orpolymeric matrix. In this case the diamond particles can protrude fromthe surface of the matrix. Such systems may be used as pad conditionersfor CMP processing. Another example of a composite is a mixture ofdiamond particle embedded in metals, ceramics, or polymers. Examplesinclude, but are not limited to, diamond-cobalt, diamond-tungstencarbide (WC), and diamond-silicon carbide composites. The diamondparticles can be of an average size greater than (>) 0.2 μm.

During CMP the diamond surface in either film, bulk or composite form isgenerally pressed on the polishing pad having the slurry between thediamond surface and the polishing pad while rotating or moving thepolishing pad relative to the diamond surface to form a smooth diamondsurface. The polishing pad can comprise a metal, ceramic, or a softpolymer including a resin, or a composite mixture of these materials. Inone embodiment the polishing pad can be a soft cloth or woolen pad, orsoft polymeric pad, each with a Shore D Hardness less than 99.

The slurry includes a plurality of slurry particles that can compriseparticles softer than diamond, have at least an outer surface softerthan diamond (e.g., diamond particles coated with a softer surface), orthe particles can comprise diamond particles averaging less than (<) 2μm in size. The slurry also includes at least one oxidizer, and at leastone acid or base, where the slurry has a pH≦3 or a pH≧11.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow chart that shows steps in an example method of CMP ofdiamond surfaces to form smooth diamond surfaces, according to anexample embodiment.

FIG. 2 is a cross sectional depiction of an article comprising asubstrate, a diamond layer having a smooth diamond surface on thesubstrate, and a diamond or semiconductor layer on the smooth diamondsurface, according to an example embodiment.

DETAILED DESCRIPTION

Disclosed embodiments are described with reference to the attachedfigures, wherein like reference numerals are used throughout the figuresto designate similar or equivalent elements. The figures are not drawnto scale and they are provided merely to illustrate the disclosedembodiments. Several aspects are described below with reference toexample applications for illustration. It should be understood thatnumerous specific details, relationships, and methods are set forth toprovide a full understanding of the disclosed embodiments.

One having ordinary skill in the relevant art, however, will readilyrecognize that the disclosed embodiments can be practiced without one ormore of the specific details or with other methods. In other instances,well-known structures or operations are not shown in detail to avoidobscuring the disclosed embodiments. The disclosed embodiments are notlimited by the illustrated ordering of acts or events, as some acts mayoccur in different orders and/or concurrently with other acts or events.Furthermore, not all illustrated acts or events are required toimplement a methodology in accordance with disclosed embodiments.

Disclosed embodiments include CMP-based methods/processes for polishingof diamond surfaces to form smooth diamond surfaces. Embodiments can beapplied to form smooth diamond surfaces from diamond single crystalsubstrates, or diamond films including super-nanocrystalline diamond(SNCD) (i.e. average grain size under 10 nm), nano-crystalline diamondgrain size (i.e., average grain size 10 to 250 nm), microcrystallinediamond (i.e. average grain size 250 nm to 250 microns), or singlecrystal diamond films (with grain size greater than 250 microns). Thetexture of the grains can be random, textured or single crystal with asingle orientation. A typical average initial (pre-CMP) root mean square(rms) surface roughness of the diamond surfaces polished by disclosedCMP polishing is at least 5 nm to 20 nm to several microns, with largergrain sizes tending to be somewhat initially rougher as compared tosmaller grain sizes.

The diamond surface to be polished can either be in the form oflayers/films with thickness ranging from 10 nm to 200 microns, or bulkmaterials with thickness exceeding 200 microns. The diamond surface isin the form of a thin film if the thickness is less than 18 micron or isin the form of a thick film if the thickness is between 20 microns to200 microns. The single crystal diamond material can be in orientationsincluding (100), (111), (110), or other crystal orientations. The singlecrystal materials may initially have a relatively low surface roughness,however, it may contain significant initial internal sub-surface damagedue to mechanical polishing of the material.

The diamond surface can be in form of composite for example, >0.2 micronsize particles on surface of a metallic matrix. In this case the diamondparticles can protrude from the surface. Such systems can be used as padconditioners for CMP processes. Other examples of disclosed compositescan include a mixture of diamond particle embedded in metals, ceramics,or polymers. Examples include, but are not limited to, diamond-cobalt,diamond-tungsten carbide (WC), diamond-silicon carbide.

Disclosed embodiments include CMP methods for processing diamondsurfaces that provide smooth diamond surfaces. As noted above, thediamond surfaces can either be in form of a thin or thick film,polycrystalline, single crystal bulk material or composite material. Thediamond surface is pressed with respect to a metal, ceramic or polymericpolishing pad having a slurry including particles and an oxidizerbetween the diamond surface and the polishing pad while rotating thepolishing pad relative to the diamond surface to polish the diamondsurface, vice versa, or rotating both simultaneously. At least an outersurface of the slurry particles and the pad can both be softer thandiamond. However, as noted above, the particles can also be uncoateddiamond particles averaging less than (<) 2 μm in size.

An unexpected result provided by disclosed methods is CMP with highdiamond removal rates (e.g., ≧20 nm/hr) using slurry particles where atleast an outer surface of the particles is softer than the diamondsurface, or the particles are diamond particles averaging less than (<)2 μm in size. Diamond coated particles can be mixed with otherparticles. Examples of non-diamond particles include alumina, siliconcarbide, silica, sapphire, quartz, other oxides, and nitrides.

The unexpected ability to polish diamond surfaces with materials softerthan diamond, or by coated diamond particles that have surfaces softerthan diamond, or by diamond particles averaging less than (<) 2 μm insize, is believed to be due to catalytic nature of disclosed polishingprocess, where the oxidizing agent catalytically breakdowns during CMPto provides in-situ reactive species. The polishing rate of diamondsurfaces using a coated diamond particle slurry containing an oxidizerand an acid or base as disclosed herein being higher as compared tousing similar diamond particles can also be attributed to the catalyticbreakdown of the oxidizing agent during CMP.

FIG. 1 is a flow chart that shows steps in an example method 100 ofchemical mechanical polishing (CMP) of diamond surfaces to form smoothdiamond surfaces, according to an example embodiment. Step 101 comprisesproviding a slurry comprising a plurality of particles, where at leastan outer surface of the particles is softer than the diamond surface orthe particles are diamond particles averaging less than (<) 2 μm insize, at least one oxidizer, and at least one acid or base. The slurryhas a pH less than or equal to (≦5), or greater than or equal to (≧) 11.The pH is generally from 1.5 to 3, or from 11 to 13.

The slurry particles can have an average particle size of ≦500 μm. Theslurry particles can comprise alumina, titania or silica particles. Theslurry particles can comprise coated diamond particles, or particleswhich are softer than diamond such as silica, alumina, boron carbide(BC), boron nitride (BN), or mixtures of these particles.

Polishing with coated diamond particles in the slurry even in presenceof chemical additives may result in surface damage in the form ofscratches or sub-surface damage below the surface of the diamondpolished surface. The surface damage can manifest as scratches and othermicrostructural defects, such as dislocations, stacking faults, surfacepits, that is created by the CMP process itself. Such defects tend tolie from 0.5 microns to 5 microns from the top surface. Thus, due topolishing, the density of defects in the near surface regions (up to 5microns) is higher than the bulk of the material. The elimination ofthese defects represents removal of sub-surface damage. Such sub-surfacedamage is of importance in large grained (grain size >0.5 micron toseveral mm) polycrystal, or single crystal diamond materials. Toeliminate or substantially reduce these defects, the slurry can compriseparticles which are softer than diamond or diamond particles that havean outer surface coated with a softer phase material as compared todiamond.

To quantify the polishing damage, a polishing damage index (PDI) is usedherein. PDI is defined by the following equation:

PDI=A−B(in units of #/cm²),

where A=average projected surface density of defects (dislocations,scratches, pits, stacking faults, etc.) in the top “y” microns ofthickness from the diamond surface being polished, and B is the averageprojected surface defect density at a distance “y” microns from thesurface of the diamond layer. The distance “y” leads is typically is “2”microns when the diamond thickness is 3 microns or more, and istypically half the thickness of the diamond film when the thickness ofthe diamond layer is less than 3 micron. The value of PDI thus providesinformation on the number of defects created by the polishing process.These defects can be measured by evaluating the surface by standardsurface and sub-surface materials characterization techniques. such asbut not limited to, optical microscopy, polarization based opticalmicroscopy, atomic force microscopy (AFM), scanning electron microscopy(SEM), transmission electron microscopy (TEM), and cathodolumiscence.Each discrete defect is numerically counted for this measurement.

The value of PDI provided by disclosed methods is generally below10⁹/cm², such as <10⁵/cm². PDI values below 10⁶/cm² correspond tosubstantially reduced surface and sub-surface damage as compared toresults provided by conventional diamond polishing methods. Undercertain disclosed polishing conditions the PDI value can be below10³/cm², including below 10²/cm².

Generally all materials are considered softer than diamond. Examples ofsofter materials include silica, alumina, zirconia, silicon nitride,silicon carbide, boron carbide, boron nitride or other nitrides,carbides, and oxides, and their mixtures and compounds. Theconcentration of particles in the slurry can vary from 0.01 weightpercent to 80 weight percent. The size of non-diamond particles can varyfrom 2 nm to 500 microns. As noted above, mixed particles can comprisecoated diamond particles mixed with non-diamond particles. The particlescan also comprise diamond particles averaging less than (<) 2 μm insize.

For polishing of diamond films and bulk diamond materials with coateddiamond particles as noted above, the diamond particles can be coatedwith insoluble compounds (insoluble in the slurry), surfactants, orother additives. The coated particles help decrease sub-surface damageand thus PDI, and can enhance the dispersion of the particles in theslurry. In case of coated diamond particles, and other particles softerthan diamond, the particle size can range from 2 nm to 500 microns, theparticle concentration can range from 0.1 weight percent to 80 weightpercent. The thickness of the coating can vary from 0.5 nm to 100microns. The coatings can be continuous or discontinuous. In the case ofdiscontinuous coatings, the area coverage is generally greater than 1percent, typically greater than 10%.

The oxidizer can include a per-compound, or comprise a transition metalwith an oxidation state of at least 3. A per-based compound is acompound that includes an element in its highest oxidation state. Someper-based oxidizer compounds include transition metal elements, such aspermanganate and non-transition elements such as perchlorate.Furthermore, the slurry can contain transition metal ions in aconcentration less than 3M, or chelating agents such as EDTA, corrosioninhibitors such azoles, and amines. Examples of transition metal elementbased oxidizers include, but are not limited to, cerium, manganese,chromium, titanium, iron, cobalt, copper, zinc, nickel, and vanadium.

Examples of per-compound oxidizers includes Potassium Permanganate:(KMnO₄), sodium Permanganate (NaMnO₄), Potassium Perchlorate (KClO₄),Potassium Periodate (KIO₄), Potassium Perbromate (KBrO₄), PotassiumPeroxide (K₂O₂), Potassium Peroxoborate (KBO₃), Potassium Peroxochromate(K₃CrO₈), Potassium Peroxodicarbonate (K₂C₂O₆), PotassiumPeroxodisulfate (K₂S₂O₈), Potassium Perrhenate (KReO₄), Potassiumperoxymonosulfate (KHSO₅), Potassium Ortho Periodate (K₅IO₅), andPotassium peroxomonosulfate (or Peroxymonosulfate) (K₂SO₅). Theoxidation state of manganese in permanganate is +7, which is the highestoxidation state for manganese. Similarly the oxidation state forchlorine in chlorate is +7, which is its highest oxidation state. Theoxidation state of the transition metal or per-based oxidizer can be atleast +3, or higher. Examples of +3 or higher oxidation state transitionmetals include V^(3+, 4+, 5+), Ti^(3+, 4+), Cr^(3+, 6+)Mn^(+3+, 4+, 7+),Fe³⁺, Ni³⁺, Co³⁺, Mo^(3+, 4+, 5+, 6+), Ru^(3+, 4+), Pd⁴⁺, Ta^(4+, 5+),W⁶⁺, Re^(4+, 6+, 7+), Au³⁺, and Zr⁴⁺. A mixture of oxidizers can also beused. The concentration of oxidizers can vary from 0.001 weight percentto maximum solubility of the oxidizer at an elevated temperature (e.g.,70° C.).

Optionally the slurry can include a salt, and/or a surfactant or asurface active polymer. The surfactant can be ionic or non-ionic, whilethe surface active polymer generally has a molecular weight exceeding500 Daltons. The surfactants and polymer can help in variety of ways toachieve disclosed smooth diamond surface. By adsorbing on to the surfaceof particles including diamond particles in one embodiment, thesurfactants or polymer decrease the friction of the polishing processthus decreasing the probability of catastrophic delamination of thediamond film. Furthermore the surfactants or polymer by absorbing on thesurface of the diamond, increases the final smoothness of the polisheddiamond surface. Finally the surfactant or polymer can increase thestability of the particles in the slurry thereby leading to more uniformpolishing process.

A variety of surfactants can also be added to disclosed slurries.Surfactants can either be cationic, anionic, zwitterionic or non-ionic.The surfactants can be used individually or in a mixed state. A list ofsurfactants that can be used with the invention are provided in a bookby M. J. Rosen, Surfactants and Interfacial Phenomena, John Wiley &Sons, 1989, hereinafter Rosen, on pages 3-32, 52-54, 70-80, 122-132, and398-401. The concentration of surfactants can vary from 0.001 times itscritical micelle concentration (CMC) to 100 times its CMC.

The slurry may also include other additives including salts, biocides,pH stabilizing agents, and soluble ions of various elements includingalkali and transitions metals. For example, the salt can comprise KI,KBr, KCO₃, KCl, NH₄I or NH₄Cl. The concentration of the salt can rangefrom 0.001M to 5M.

Step 102 comprises pressing the diamond surface with a pad comprising ofa metal, metal ceramic composite, metal polymeric composite, diamondparticle impregnated metal, soft cloth, woolen pad or polymericpolishing pad having the slurry in between while rotating the padrelative to the diamond surface to form a smooth diamond surface. Thepad has a Shore D Hardness less than 99.

If the thickness of the diamond films is less than 20 microns (a thindiamond film), for example 18 microns, delamination of the thin diamondfilm from the substrate during the polishing process can become moreprevalent. Although generally any polishing pad can also be used in thiscase, it can be helpful for reducing delamination to use a cloth, woolenor resin pads, or soft polymeric pad with a Shore D hardness notexceeding 99, typically <90. The polymeric pads can comprisepolyurethane-based compounds, or other crosslinked polymers. The padscan be also composite of these materials. To further reduce delaminationeffects for thin diamond films, a surfactant can be added to the slurryand a soft polymeric, woolen, or cloth, or resin based polishing padscan be used. Such a polishing pad may or may not be impregnated withparticles, such as diamond particles.

The pad pressure can range from 0.5 psi to less than 500 psi. In someembodiments the polishing pressure used is less than 10 psi, such asfrom 1 psi to 8 psi. At pressures in the lower end of the range, theremoval rates are lower. The removal rate at the higher end of the rangeis higher, however diamond films may delaminate under these conditions.The linear velocity can range from 0.05 m/sec to 100 m/sec. At lowervelocities the removal rate is low compared to higher end of the range(>1 m/sec). However at higher linear speeds the films may delaminate orthe pad may be eroded at a much higher rate. As the polymeric pad isviscoelastic in nature, the low linear velocities also help the pad todeform to the curvature of the diamond film on the substrate. Therotation speed can range from 5 rpm to 5000 rpm during the polishingprocess. The removal rate is expected to increase with higher rpm's,however at higher rpm the pad may not be able to deform to polishedbowed surfaces or it may be eroded very rapidly. CMP is generallyperformed at a temperature ≦70° C., such as <40° C. (e.g., in atemperature range of 20 to 30° C. (room temperature)). The diamondsurface can also be exposed to radiation in a wavelength range from theinfrared to the ultraviolet during CMP.

As noted above, the polishing pad can be a soft cloth or woolen pad, orsoft polymeric pad with Shore D Hardness less than 99, typically <90.Optionally, the pad can comprise two or more layers with the hardness ofthe layer contacting the diamond substrate surface to be at least aShore D hardness 10 greater than the non-contacting polymer layers. Thethickness of the polymer pad can be at least 0.05 mm to up to about 20mm.

The polishing pad can comprise a metal. In this embodiment, the metalpad can generally comprise any metal ranging with a Knoop hardness of 50kg/mm² to 1500 kg/mm². Examples of metal pads include metal surfacesmade of tin, copper, iron, steel, brass etc. Examples of ceramic padsinclude, alumina, titania, zirconia or, carbides, silicon nitride andother nitrides. Optionally the metal, ceramic or polymeric pad may beimpregnated with particles ranging in hardness from diamond (Knoophardness 10,000 kg/mm²) to soft metallic or ceramic particles withhardness greater than 100 kg/mm². Optionally resin bonded pads may beused with or without impregnated said particles. Particles impregnatedin the polishing pad can help to increase the abrasive nature of thepad, and thus can accelerate the removal rate of the slurry. The resinbonded pads can include metal or ceramic powders such as copper, tin,antimony, etc. The metal pad can comprise a single phase of metal ormetal alloy such as brass, cast iron, tin, copper, and alloys orcomposites.

In some embodiments, the polishing pad comprises a soft and porouspolymer. For example, the material of the soft polymer polishing pad canhave a density less than 0.8 g/cm³ or a hardness less than 90 SHORE D,such as polyethylene. Example of soft polymeric pads include the D100™pad provided by Cabot Microelectronics (Aurora, Ill.), the SUBA™ 4 andIC1000™ pad provided by Rodel, Inc (Phoenix, Ariz.). The SUBA™ 4 pad isa polyurethane impregnated polyester felt pad, and the IC1000™ pad is aperforated polyurethane hard top polishing pad. When polishing diamondthin or thick films and polycrystalline or single crystal bulk diamondmaterials or a composite diamond material, a soft pad (woolen, cloth,resin, or polymer) def^(i)ned herein to have a Shore D hardness lessthan 99, diamond particle or diamond coated particle or mixed particles(diamond and other particles) of size ranging from 2 nm to 500 micronscan be used.

As noted above, the CMP methods disclosed herein may be based on thein-situ catalytic breakdown of the oxidizing agent which providesreactive species which increases the diamond removal rate. The catalyticaction can be further enhanced by use of a temperature above roomtemperature (e.g., 35 to 90° C.), rubbing action during the CMP process,the presence of insoluble compounds and elements of transition metals,coating of the surface of slurry particles with insoluble elements orcompounds of transition metals, the presence of soluble transition metalions, an increase in friction during polishing, formation of insolubletransition metal compound during polishing as a result of breakdown ofthe oxidizer, coating of the polishing pad surface with a transitionmetal oxide or an insoluble compound, or illuminating the polishingprocess with a optical lamp whose radiation output can be varied inwavelength range from ultraviolet to the infrared.

The catalytic action can be accelerated by a local temperature increasethat can occur during the polishing process itself. In anotherembodiment, the temperature can be increased by providing an externalheat source, such as a heated slurry, heating of the pad and polishingapparatus using lamps, or a resistively heated source. The catalyticaction can be accelerated also by the presence of soluble ions (e.g.,transition metal ions of manganese, zinc, chromium, iron, cobalt,copper), insoluble soft surface compositions (e.g., transition metal(Mn, Cu, Zn, Co, Fe, Ni) oxides, nitrides, chlorides, sulfates, nitratescarbonates (e.g., MnO₂, MnCl₃, TiO₂, CuO), or transition metals (Fe, Mn,Zn, Co, Ag)) during the polishing process.

If the thickness of the diamond film is less than 20 microns (defined asdiamond thin films), for example 15 microns, issues of delamination ofthe film from the substrate can become more prevalent. In this caseparticles in the slurry of any size or any hardness, and composition,and concentration can be used in the slurry. However in one embodimentthe slurry comprises of plurality of non-diamond particles (hardness 100kg/mm² to 1000 kg/mm², size 2 nm to 500 microns, concentration 0.01weight % to 80 weight percent), and/or diamond particles limited to sizeless than 2 microns, an oxidizer containing a per compound or transitionmetal element, and an acid so that the pH of the slurry is less than 3,such as 1.5 to 3.

Diamond films grown on various substrates are expected to causesignificant curvature of the substrates. The curvature arises due tointrinsic growth and thermal mismatch stresses that may lead tocurvature of the diamond film containing substrate. To ensure that thediamond films containing substrate is polished uniformly across thewafer, a polymeric pad with Shore D hardness less than 99 or compositepad and thickness ranging from 1 micron to 10 cm can be used. Due toprior or mechanical polishing hard diamond polishing the density ofdefects in the near surface regions (up to 5 microns) is higher than thebulk of the material. The partial or whole reduction of these defectsrepresents removal of sub-surface damage. The partial or whole removalof the scratches and surface defects from the near surface regionsrepresents removal of sub-surface damage.

FIG. 2 is a cross sectional schematic view of an article 200 comprisinga substrate 201, a diamond layer 202 having a smooth diamond surface 203on the substrate 201, and a capping layer 205 comprising a diamond or asemiconductor on the smooth diamond surface 203. A plurality ofelectronic devices (e.g., transistors) 208 are formed in or on thecapping layer 205. Substrate 201 can comprise various substratesincluding silicon, diamond, GaN, AlGaN or SiC. When the capping layer205 comprises a semiconductor, the semiconductor can comprisesemiconductors including silicon, GaN, AlGaN, SiC, or TiN. In oneembodiment the diamond layer 202 comprises cobalt-diamond,nickel-diamond, or diamond particles protruding from a matrix comprisingmetals or ceramics, such nickel or tungsten carbide. In anotherembodiment the substrate 201 comprises a single crystal diamondsubstrate that includes the diamond layer 202 having a smooth diamondsurface 203.

The smooth diamond surface 203 has (i) rms surface roughness less than(<) 15 nm for an average grain size greater than (>) 0.5 μm, an rmssurface roughness less than (<) 10 nm for an average grain size between50 nm and 0.5 μm, and an rms surface roughness less than (<) 5 nm for anaverage grain size less than (<) 50 nm, and (ii) a polishing damageindex (PDI) of less than (<) 10⁹ per cm². In one embodiment where theaverage grain size is greater than (>) 100 nm, the PDI is less than (<)10⁶/cm² and the rms surface roughness is less than (<) 1 nm.

Electronic devices 208 can benefit from the high thermal conductivity ofthe diamond layer 202 as well as the capping layer 205 when the cappinglayer 205 comprises a diamond layer, which can provide a heat spreadingfunction to help dissipate heat generated by the electronic devices 208during operation. In another embodiment the diamond layer 202 is apatterned layer comprising a plurality of diamond islands.

EXAMPLES

Disclosed embodiments are further illustrated by the following specificExamples, which should not be construed as limiting the scope or contentof the disclosed embodiments in any way. The temperature used wasapproximately 25° C. for all Examples.

Example 1

Diamond samples having different thickness were polished with a CMPslurry composition that comprised i) a liquid (e.g. water) carrier, andan oxidizer comprising the transition metal per-compound potassiumpermanganate. Experiments performed using Buehler Ecomet 4/Automet 2polisher. The potassium permanganate oxidizer concentration was 0.4molar, and 10% alumina particles with a particle size of around 300 nmwere used. Nitric acid (HNO₃) was included to provide a pH for theslurry of 2. The polishing parameters used for polishing was pressure 10psi, pad linear velocity 1 m/sec, and an IC1000 pad polymeric padcomposed of polyurethane.

RMS Type of Material roughness of Subsurface Diamond Removal surfaceafter damage/ S.No Sample rate polishing Scratches 1 Thin film 100nm/hr  7 A No (300 nm) 2 Thick film 80 nm/hr 3 A No (Thickness film 100micron) 3 Bulk sample 70 nm/hr 1 A No (300 microns) 4 Diamond 30 nm/hr30 nm No Composite 5 (111) Diamond <10 nm/hr   3 A No

Example 2

Diamond samples having different crystallite size were polished with aCMP slurry composition that comprised i) a liquid (e.g. water) carrier,and an oxidizer being the per-compound potassium permanganate orpotassium persulfate. Experiments were performed using Buehler Ecomet 4and Automet 2 polisher. The oxidizer concentration was 0.4 mole/liter,and 10% Alumina particles with a particle size of 300 nm, or 0.25 μmdiamond particles with a concentration of 2 percent, or a mixture ofboth, was used. Nitric acid was used to adjust the pH of the slurry to2. The polishing parameters used for polishing was pressure 10 psi, padlinear velocity 1 m/sec, and a Cabot D100 pad. The polishing runs wereconducted for 200 minutes.

Particles RMS of Subsurface S. Type of Diamond in the Removal surfaceafter damage/ No Sample slurry rate polishing scratches 1 Super Nano-Alumina 100 nm/hr 5 A No Crystalline diamond (grain size 5 nm) 2Nano-Crystalline Alumina 120 nm/hr 3 A No diamond (grain size 250 nm) 3Micro-crystalline Alumina 80 nm/hr 25 A No diamond (1/4 micron to 25micron) 4 Large grain Alumina 70 nm/hr 35 A No diamonds (25 to 100micron) 5 Single crystalline 1/4 micron 25 nm/hr 1.5 A Yes samplediamond 6 Single crystal 1/4 micron 75 1.5 A Yes diamond diamond +Alumina 7 Diamond-Cobalt Alumina 30 nm/hr 30 nm No composite

Example 3

A diamond 1 cm×1 cm microcrystalline sample was polished with a CMPslurry composition that comprised of i) a liquid (e.g. water) carrier,and an oxidizer being the per-compound potassium persulfate. Experimentswere performed using Buehler Ecomet 4 and Automet 2 polisher. Theoxidizer concentration was 0.4 molar, and the particles were 2%, 0.25micron diamond particle. Nitric acid was used to provide a pH of 2. Thepolishing parameters using for polishing was pressure 10 psi, pad linearvelocity 1 m/sec, on different pads as described below. The polishingruns were conducted for 60 minutes.

S. No Type of Pads Removal rate Type of Pad 1 Politex  20 nm/hr Polymer2 Suba IV  40 nm/hr Polymer 3 D100 210 nm/hr Polymer 4 IC 1000 240 nm/hrPolymer 5 Cast Iron disc 280 nm/hr Metal 6 Ceramic Disc 300 nm/hrCeramic 7 Resin bonded copper pad 300 nm/hr Metal 8 Diamond impregnated300 nm/hr Metal metal pad

Example 4

A diamond 1 cm×1 cm polycrystalline sample was polished with a CMPslurry composition that comprised i) a liquid (e.g. water) carrier, andan oxidizer being selected from the per-compounds shown in table below.Experiments were performed using Buehler Ecomet 4/Automet 2 polisher.Different oxidizer with concentration of 0.4 mole/liter along with 2%, ¼μm average size diamond particles were used in the slurry for polishing.Nitric acid was used to change the pH of the slurry to 2. The polishingparameters used for polishing were pressure 10 psi, pad linear velocity1 m/sec, on an IC1000 pad. The polishing runs were conducted for 60minutes.

S. No Per-compound oxidizer Removal rate 1 Potassium Permanganate 140nm/hr 2 Potassium Peroxymonosulfate 180 nm/hr 3 Potassium perfsulfate240 nm/hr 4 Hydrogen peroxide 140 nm/hr 5 Potassium Periodate 140 nm/hr6 Sodium Hypochlorite 140 nm/hr

Example 5

A diamond 1 cm×1 cm polycrystalline sample was polished with a CMPslurry composition that comprised i) a liquid (e.g. water) carrier, andan oxidizer with the per-compound potassium persulfate. Experiments wereperformed using Buehler Ecomet 4 and Automet 2 polisher. The oxidizerconcentration was 0.2 mole/liter and different slurry particles listedin table below were used. Nitric acid was used to change the pH of theslurry to 2. The polishing parameters used for polishing was pressure 10psi, pad linear velocity 1 m/sec, on an IC 1000 pad. The polishing runswere conducted for 60 minutes.

Particles Removal rate 10% Silica (135 nm) 10 nm/hr 10% Silicon carbide(8 micron) 60 nm/hr 10% Alumina (800 nm) 50 nm/hr

Example 6

A diamond 1 cm×1 cm polycrystalline sample was contacted with a CMPslurry composition that comprised of i) a liquid (e.g. water) carrierand an oxidizer with a per-compound persulfate. Experiments performedusing polisher from Buehler Ecomet 4 and Automet 2 polisher. Theoxidizer concentration was 0.2 mole/liter, different particles coatedwith transition metal oxide (MnO₂) listed in table below were used. Thepolishing parameters used were pressure 10 psi, pad linear velocity 1m/sec, on an IC1000 pad. The polishing runs were conducted for 60minutes.

Particles Removal rate 10% Silica (135 nm) 15 nm/hr 10% Silicon carbide(4-8 micron) 70 nm/hr Alumina (300 nm) 60 nm/hr 1 micron diamond 300nm/hr 

Example 7

A diamond 1 cm×1 cm polycrystalline sample was polished with a CMPslurry composition that comprises of i) a liquid (e.g. water) carrierand an oxidizer with compound of a per-compound potassium persulfate.Experiments were performed using Buehler Ecomet 4 and Automet 2polisher. The oxidizer concentration was 0.2 molar, and 1% 1 microndiamond particles and different surfactants listed in the table wereused. The polishing parameters used were pressure 10 psi, pad linearvelocity 1 m/sec, and an IC1000 pad was used. The polishing runs wereconducted for 60 minutes.

Surfactant Removal rate 0.1 wt % secondary alkane 260 nm/hr sulphonatesodium salt 0.1 wt % Poly Acrylic acid 180 nm/hr 0.1 wt % CTAB 240 nm/hr0.1 wt % Sodium dodecyl 160 nm/hr sulphate

Example 8

A diamond 1 cm×1 cm polycrystalline sample was polished with a CMPslurry composition that comprises of i) a liquid (e.g. water) carrier,and an oxidizer with a per-compound permanganate. Experiments wereperformed using Buehler Ecomet 4 and Automet 2 polisher. The oxidizerconcentration was 0.2 molar, and 1% ¼ micron diamond particles wereused. The polishing pressure was 5 psi and the pad linear velocity was 1m/sec, and a Cabot D100 pad was used for experiments. The polishing runswere conducted for 60 minutes with different slurry pH as shown in tablebelow:

pH of the Slurry Removal rate 1 90 nm/hr 2 60 nm/hr 3 60 nm/hr 5 20nm/hr 9 20 nm/hr 12 20 nm/hr 13 20 nm/hr

Example 9

Diamond particles protruding from a metal plate (>4 inch in diameter)was polished with a CMP slurry composition that comprises of i) a liquid(e.g. water) carrier, and an oxidizer with the per-compound potassiumpersulfate. Experiments were performed using Buehler Ecomet 4 andAutomet 2 polisher. The oxidizer concentration was 0.2 molar, with 1% ¼micron diamond slurry particles. The polishing pressure was 5 psi, thepad linear velocity 1 m/sec, and a Cabot D100 pad was used. Thepolishing runs were conducted for 60 minutes. The diamond particlesprotruding from the metal plate had a height between 10 micron and 500micron. The polishing rate of the diamond particles was 100 nm/hr.

While various embodiments of the invention have been described above, itshould be understood that they have been presented by way of exampleonly, and not limitation. Numerous changes to the disclosed embodimentscan be made in accordance with the disclosure herein without departingfrom the spirit or scope of the disclosed embodiments. Thus, the breadthand scope of embodiments of the invention should not be limited by anyof the above explicitly described embodiments. Rather, the scope of theinvention should be defined in accordance with the following claims andtheir equivalents.

Although the embodiments of invention have been illustrated anddescribed with respect to one or more implementations, equivalentalterations and modifications will occur to others skilled in the artupon the reading and understanding of this specification and the annexeddrawings. In addition, while a particular feature may have beendisclosed with respect to only one of several implementations, suchfeature may be combined with one or more other features of the otherimplementations as may be desired and advantageous for any given orparticular application.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting to embodiments ofthe invention. As used herein, the singular forms “a,” “an,” and “the”are intended to include the plural forms as well, unless the contextclearly indicates otherwise. Furthermore, to the extent that the terms“including,” “includes,” “having,” “has,” “with,” or variants thereofare used in either the detailed description and/or the claims, suchterms are intended to be inclusive in a manner similar to the term“comprising.”

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which embodiments of the inventionbelongs. It will be further understood that terms, such as those definedin commonly used dictionaries, should be interpreted as having a meaningthat is consistent with their meaning in the context of the relevant artand will not be interpreted in an idealized or overly formal senseunless expressly so defined herein.

1. A method of chemical mechanical polishing (CMP) a diamond surfacecomprising: providing a slurry comprising a plurality of particles, atleast one oxidizer, and at least one acid or base, wherein said slurryhas a pH less than or equal to (≦) 3 or greater (>) than 11, wherein atleast an outer surface of said plurality of particles is softer thansaid diamond surface or said plurality of particles are diamondparticles averaging less than (<) 2 μm in size; pressing said diamondsurface with a pad having a Shore D Hardness less than (<) 99 havingsaid slurry in between while rotating said pad relative to said diamondsurface to form a smooth diamond surface having a root mean square (rms)surface roughness less than 15 nm.
 2. The method of claim 1, whereinsaid pad comprises a soft cloth, metallic woolen pad or polymericpolishing pad with said Shore D hardness less than (<)
 90. 3. The methodof claim 1, wherein said plurality of particles comprise alumina,titania or silica.
 4. The method of claim 1, wherein said oxidizercomprises a transition metal compound or a per compound.
 5. The methodof claim 4, wherein said oxidizer comprises KMnO₄ or a K₂S₂O₈ compound.6. The method of claim 1, wherein said diamond surface is a composite ofcobalt-diamond or nickel-diamond, or diamond particles protruding from amatrix.
 7. The method of claim 1, wherein a polishing pressure used forsaid pressing is less than 10 psi.
 8. The method of claim 1, whereinsaid slurry comprises at least one surfactant.
 9. A method of chemicalmechanical polishing (CMP) a diamond surface, comprising: providing aslurry comprising a plurality of particles, wherein at least an outersurface of said plurality of particles is softer than said diamondsurface, at least one oxidizer comprising a transition metal compound ora per compound, and at least one acid, wherein said slurry has a pH lessthan or equal to (≦) 3; pressing said diamond surface with a soft cloth,or metallic woolen pad or polymeric polishing pad having a Shore DHardness less than (<) 99 with said slurry in between while rotatingsaid polishing pad relative to said diamond surface to form a smoothdiamond surface having a root mean square (rms) surface roughness lessthan (<) 10 nm.
 10. The method of claim 9, when a polishing pressureused for said pressing is less than 10 psi.
 11. The method of claim 9,wherein said slurry comprises at least one surfactant.
 12. The method ofclaim 9, wherein said rms surface roughness is less than (<) 1 nm.